CN105924340A - Method for synthesizing natural anisaldehyde by catalyzing hydrogen peroxide to oxidize anethole - Google Patents
Method for synthesizing natural anisaldehyde by catalyzing hydrogen peroxide to oxidize anethole Download PDFInfo
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of CHx-moieties
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Abstract
The invention discloses a method for synthesizing natural anisaldehyde by catalyzing hydrogen peroxide to oxidize anethole. In the absence of a solvent, sodium metavanadate serves as a catalyst, hexadecyl trimethyl ammonium bromide serves as a phase transfer catalyst, and natural anisaldehyde is synthesized by oxidizing anethole with hydrogen peroxide. Compared with the prior art, the method has the advantages that the technology is simple; no solvent is used in the reaction process, so that production cost is reduced, and the influence on the environment is avoided; the reaction temperature is low, the reaction time is short, little energy is consumed, and the natural degree of anisaldehyde is easily maintained; the catalysts have high catalyzing efficiency on anethole, have good selectivity on anisaldehyde, and can be recycled; a large amount of anethole can be handled, and the production efficiency can be easily improved.
Description
Technical field
The invention belongs to the preparation method of a kind of chemical products.Specifically a kind of catalyzing hydrogen peroxide oxidation trans-anethole closes
The method becoming natural anisaldehyde.
Background technology
Anisaldehyde is a kind of important essence and flavoring agent, can be widely used in food as spice and chemical intermediate
The industries such as product, pharmacy, daily use chemicals.Anisaldehyde fragrance with natural anethole as raw material production is optimal.Work at present
It is to use MnO that industry produces the main method of anisaldehyde2/H2SO4(Li Zhengqiu, breathes out into make oxidizing trans-anethole
Bravely, horse one is waited quietly, and manganese dioxide trans-anethole prepares the technical study of anisaldehyde, chemistry of forest product and industry,
2009,29(4):59-62.).Ozonation and electrochemical oxidation process are possible alternative methods.But
These methods are similar with manganese dioxide, all have that equipment cost is big, power consumption is high, by-product is many and environment is dirty
Contaminate serious problem (Li Yunyan, Li Minxian, trans-anethole oxidative synthesis anisaldehyde process progress, chemical intermediate,
(01), 12-15 (2010)).Although the bioconversion utilizing trans-anethole produces anisaldehyde can avoid oxygen
Some shortcomings of change method, but the biotransformation method conversion ratio owing to having reported is low, and reaction condition need to strictly control,
Still it is difficult to obtain commercial Application.The most rising is to use Green Oxidant hydrogen peroxide to aoxidize
Reaction.It is catalyzed H with vfanadium compound both at home and abroad2O2The report of oxidizing process synthesis anisaldehyde.Xiao Yi is to contain
The aromatic acid vanadic salts catalysis 50%H of machine alkali2O2Oxidation trans-anethole synthesis anisaldehyde, achieves higher effect (Yi
Xiao,Hongmei Huang.Et al.Oxidation of anethole with hydrogen peroxide
catalyzed by oxovanadium aromatic carboxylate complexes.,Catalysis
Communications, (10), 29-32 (2008), Xiao Yi, yellow Fructus Mume, Yin Dulin etc., organic base is situated between
The aromatic carboxylic acids vanadyl catalyzing hydrogen peroxide oxidation of anethole through entered, Journal of Molecular Catalysis, 25 (03), 233-238
(2011)).But in this method, catalyst synthesis processes is complicated and is difficult to reclaim, reaction dissolvent acetonitrile poison
Property relatively big, the H of employing2O2Concentration is higher, adds complexity and the insecurity of technique.We the most once opened
The technique having sent out ferric vandate catalyzing hydrogen peroxide oxidizing process, although solve asking of catalyst recycling
Topic, but organic solvent dioxane need to be used, and trans-anethole treating capacity is little, production efficiency is low, has influence on this
Popularization (Yao Xingdong, Peng Caihua, Nie Yuanmei etc., a kind of side being prepared natural anisaldehyde by anethole of technique
Method, patent of invention ZL201310180914.6).
Summary of the invention
It is an object of the invention to provide a kind of reaction condition gentleness, conversion ratio and yield is the highest, catalyst can
The method of reusable a kind of catalyzing hydrogen peroxide oxidation trans-anethole synthesis of natural anisaldehyde.
The technical scheme is that
The method of a kind of catalyzing hydrogen peroxide oxidation trans-anethole synthesis of natural anisaldehyde, solvent-free and certain
At a temperature of, use sodium metavanadate be catalyst, cetyl trimethylammonium bromide be phase transfer catalyst, urge
The method changing hydrogen peroxide oxidation trans-anethole synthesis of natural anisaldehyde.Specifically comprise the following steps that
1) by 5mL trans-anethole, 0.0300～0.0600g sodium metavanadate and 0.0300～0.0600g hexadecane
Base trimethylammonium bromide joins in round-bottomed flask, and to add 5～11mL mass percentage concentration be 30% mistake
Hydrogen peroxide solution, is that 6mol/L hydrochloric acid solution regulates reactant liquor pH to 0.60 by concentration.
2) above-mentioned round-bottomed flask is placed in 25～40 DEG C of water bath with thermostatic control magnetic stirring apparatuss, heating in water bath for reaction,
After reaction 1～5h, take 1.00mL reactant liquor, use the extraction of 10.00mL ethyl acetate, obtain containing mesh
The organic facies of mark product anisaldehyde；Use gas chromatography detection extract organic facies, measure trans-anethole conversion ratio
And the selectivity of anisaldehyde.
Analytical conditions for gas chromatography is as follows: SE-54 capillary column 30m (length) × 0.25mm is (interior
Footpath) × 0.25 μm (thickness), fid detector, injector and detector temperature 250 DEG C, post
Temperature 150 DEG C.N2Make carrier gas, flow velocity 1mL/min.Split sampling, split ratio 40:1.
3) containing substantial amounts of catalyst and phase transfer catalyst in the aqueous phase obtained after extraction, through boiling off
Use can be continued cycling through after water.
The present invention has the following advantages compared with the prior art:
1. present invention process is simple.
2. course of reaction does not use solvent, reduces production cost and avoids the impact on environment yet.
3. heating-up temperature is low, and the time is short, and energy consumption is little and is conducive to keeping the natural degree of anisaldehyde.
4. catalyst can be recycled, and have higher catalytic efficiency to trans-anethole, and p-anisaldehyde also has relatively
Good selectivity.
5. in reaction, trans-anethole concentration is high, has higher production efficiency, is more beneficial for realizing industrialization.
Detailed description of the invention
The present invention is to utilize sodium metavanadate for catalyst, and cetyl trimethylammonium bromide is phase transfer catalysis
Agent, 30%H2O2Anisaldehyde is synthesized for oxidizing trans-anethole.Trans-anethole of the present invention (99%, I
Fourth), sodium metavanadate (AR, traditional Chinese medicines group), cetyl trimethylammonium bromide (AR, traditional Chinese medicines group), 30%
H2O2(AR, Chengdu Ke Long chemical reagent factory), concentrated hydrochloric acid (>=37.5%, Chengdu Ke Long chemical reagent factory).
Gas chromatographic analysis uses SP 6890 gas chromatograph (the Shandong Lunan auspicious rainbow limited public affairs of chemical industry instrument
Department), constant temperature water bath magnetic agitation is in DF-101S type heat collecting type magnetic force heating stirrer (Jintan City of Jiangsu Province
Medical Instruments factory) on carry out.
It is as follows that reaction condition optionally affects situation to trans-anethole conversion ratio and anisaldehyde:
1. trans-anethole conversion ratio and anisaldehyde are optionally affected by phase transfer catalyst kind
By 0.0600g sodium metavanadate, 9.00mL 30%H2O2Solution and 0.06ml 1:1 hydrochloric acid solution add
In the round-bottomed flask equipped with 5.00ml (about 5.0047g) trans-anethole, it is separately added into 0.0500g different types of
Phase transfer catalyst, is placed in above-mentioned round-bottomed flask in 35 DEG C of water bath with thermostatic control magnetic stirring apparatuss, heating in water bath
Reaction, after reaction 3h, takes 1.00ml reactant liquor, uses 10.00ml ethyl acetate to extract, stratification,
Obtain the organic facies containing target product anisaldehyde；Use gas chromatography detection extract organic facies, calculate
Trans-anethole conversion ratio and the selectivity of anisaldehyde, result is as shown in table 1.
Trans-anethole conversion ratio and anisaldehyde are optionally affected by table 1 phase transfer catalyst kind
As shown in Table 1, the phase transfer catalyst of cationic is more beneficial for improving conversion ratio and the Fructus Foeniculi of trans-anethole
The selectivity of aldehyde, cetyl trimethylammonium bromide is as the best results of phase transfer catalyst.
2. trans-anethole conversion ratio and anisaldehyde are optionally affected by reactant liquor pH
Take trans-anethole 5.00ml (5.0027g), sodium metavanadate 0.0500g, phase transfer catalyst (hexadecane
Base trimethylammonium bromide) 0.0500g, 30% hydrogen peroxide 9.00ml are in 100ml round-bottomed flask, with not
The 1:1 hydrochloric acid solution regulation reactant liquor pH of same volume, is placed in the water bath with thermostatic control of 35 DEG C by above-mentioned round-bottomed flask
Reacting 3h in magnetic agitation pot, reaction pipettes 1.00mL reactant liquor and extracts with 10mL ethyl acetate after terminating
After, use GC to carry out detecting trans-anethole conversion ratio and anisaldehyde selectivity.Measurement result is as shown in table 2 below:
Table 2 acidic buffer solution addition affect result
As shown in Table 2, when hydrochloric acid solution addition is 0.06mL, the selectivity of anisaldehyde is optimal, this
Time reactant liquor pH be 0.60～0.65.
3. trans-anethole conversion ratio and anisaldehyde are optionally affected by reaction temperature
Take trans-anethole 5.00mL, sodium metavanadate 0.0500g, phase transfer catalyst (cetyl trimethyl bromination
Ammonium) 0.0500g, 30% hydrogen peroxide 9.00mL, 1:1 hydrochloric acid solution 0.06mL join 100mL round bottom
In flask, after 25～40 DEG C of stirred in water bath react 3h, sampling 1.00mL reactant liquor is through 10.00mL
After ethyl acetate extraction, with trans-anethole in gas chromatography determination organic facies and the concentration of anisaldehyde, result such as table
Shown in 3:
Trans-anethole conversion ratio and anisaldehyde are optionally affected by table 3 reaction temperature
| Reaction temperature (DEG C) | 25 | 30 | 35 | 40 |
| Trans-anethole conversion ratio (%) | 54.33 | 57.78 | 86.76 | 98.37 |
| Anisaldehyde selectivity (%) | 35.69 | 51.29 | 51.55 | 47.39 |
As shown in Table 3, along with the raising of reaction temperature, trans-anethole conversion ratio presents increasing trend, but anisaldehyde
Selectivity temperature be in the range of 30～35 DEG C preferably.
4.H2O2Trans-anethole conversion ratio and anisaldehyde are optionally affected by consumption
Take trans-anethole 5.00mL, sodium metavanadate 0.0500g, phase transfer catalyst (cetyl trimethyl bromination
Ammonium) 0.0500g, 1:1 hydrochloric acid solution 0.06mL in 100ml round-bottomed flask, add different volumes 30%
H2O2Solution, in 35 DEG C of heating in water bath and stir reaction 3h after, pipette 1.00mL reactant liquor with 10.00mL
Ethyl acetate extracts, with trans-anethole in gas chromatography determination organic facies and the concentration of anisaldehyde, and result such as table 4
Shown in:
Table 4 30%H2O2Trans-anethole conversion ratio and anisaldehyde are optionally affected by consumption
| 30%H2O2Addition (mL) | 5.00 | 7.00 | 9.00 | 11.00 |
| Trans-anethole conversion ratio (%) | 81.35 | 85.86 | 86.76 | 81.43 |
| Anisaldehyde selectivity (%) | 42.48 | 44.35 | 51.55 | 43.94 |
As shown in Table 4, H2O2When addition is 9.00mL, the selectivity of anisaldehyde is optimal.
5. trans-anethole conversion ratio and anisaldehyde are optionally affected by sodium metavanadate consumption
Take trans-anethole 5.00mL, 30%H2O29.00mL, phase transfer catalyst (cetyl trimethylammonium bromide)
0.0500g, 1:1 hydrochloric acid solution 0.06mL is in 100ml round-bottomed flask, and adds 0.03～0.06g
Sodium metavanadate, in 35 DEG C of heating in water bath and stir reaction 3h after, pipette 1.00mL reactant liquor with 10.00mL
Ethyl acetate extracts, with trans-anethole in gas chromatography determination organic facies and the concentration of anisaldehyde, and result such as table 5
Shown in:
Trans-anethole conversion ratio and anisaldehyde are optionally affected by table 5 sodium metavanadate consumption
As shown in Table 5, along with the increase of sodium metavanadate consumption, the selectivity of trans-anethole conversion ratio and anisaldehyde is equal
Presenting increasing trend, sodium metavanadate consumption is more than 0.0500g, good catalytic activity.
6. trans-anethole conversion ratio and anisaldehyde are optionally affected by cetyl trimethylammonium bromide consumption
Weigh trans-anethole 5.00mL, sodium metavanadate 0.0600g, 30%H2O29.00mL, 1:1 hydrochloric acid solution
0.06mL, in 100ml round-bottomed flask, adds the phase transfer catalyst (cetyl of 0.03～0.06g
Trimethylammonium bromide), in 35 DEG C of heating in water bath and stir reaction 3h after, pipette 1.00mL reactant liquor with
10.00mL ethyl acetate extracts, with trans-anethole in gas chromatography determination organic facies and the concentration of anisaldehyde, knot
Fruit is as shown in table 6:
Trans-anethole conversion ratio and anisaldehyde are optionally affected by table 6 phase transfer catalyst consumption
| Phase transfer catalyst consumption (g) | 0.03 | 0.04 | 0.05 | 0.06 |
| Trans-anethole conversion ratio (%) | 76.77 | 84.87 | 96.26 | 95.69 |
| Anisaldehyde selectivity (%) | 33.82 | 42.43 | 55.58 | 31.15 |
As shown in Table 6, when phase transfer catalyst consumption is 0.05g, the selectivity of anisaldehyde is optimal.
7. trans-anethole conversion ratio and anisaldehyde are optionally affected by the response time
Take 5.00mL trans-anethole, sodium metavanadate 0.0600g, phase transfer catalyst 0.0500g, 30%H2O2
9.00mL, 1:1 hydrochloric acid solution 0.06mL is in 100ml round-bottomed flask, in 35 DEG C of heating in water bath and stir
Reaction, samples 1.00mL every 1h, after 10.00mL ethyl acetate solution extracts, with gas chromatography
Measuring trans-anethole and the concentration of anisaldehyde in organic facies, the conversion ratio of trans-anethole and the selectivity of anisaldehyde are in time
Change as shown in table 7:
Trans-anethole conversion ratio and anisaldehyde are optionally affected by table 7 response time
As shown in Table 7, when the response time is 3h, the selectivity of anisaldehyde is best, trans-anethole also fundamental reaction
Completely.
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1
The method of a kind of catalyzing hydrogen peroxide oxidation trans-anethole synthesis of natural anisaldehyde, solvent-free and certain
At a temperature of, use sodium metavanadate be catalyst, cetyl trimethylammonium bromide be phase transfer catalyst, urge
The method changing hydrogen peroxide oxidation trans-anethole synthesis of natural anisaldehyde.Specifically comprise the following steps that
1) by 5.00mL trans-anethole, 0.0500g sodium metavanadate and, 0.0500g cetyl trimethyl bromination
Ammonium joins in round-bottomed flask, and to add 9.00mL mass percentage concentration be 30% hydrogenperoxide steam generator, uses
Concentration is that 6mol/L hydrochloric acid solution regulates reactant liquor pH to 0.60.
2) above-mentioned round-bottomed flask is placed in 35 DEG C of water bath with thermostatic control magnetic stirring apparatuss, heating in water bath for reaction, instead
After answering 3h, take 1.00mL reactant liquor, use the extraction of 10.00mL ethyl acetate, obtain containing target product
The organic facies of anisaldehyde；Use trans-anethole and the concentration of anisaldehyde in gas chromatography detection extract organic facies,
Measuring trans-anethole conversion ratio is 89.66%, and the selectivity of anisaldehyde is 51.55%.
3) containing substantial amounts of catalyst and phase transfer catalyst in the aqueous phase obtained after extraction, through boiling off
Use can be continued cycling through after water.
Embodiment 2
The method of a kind of catalyzing hydrogen peroxide oxidation trans-anethole synthesis of natural anisaldehyde, solvent-free and certain
At a temperature of, use sodium metavanadate be catalyst, cetyl trimethylammonium bromide be phase transfer catalyst, urge
The method changing hydrogen peroxide oxidation trans-anethole synthesis of natural anisaldehyde.Specifically comprise the following steps that
1) by 5mL trans-anethole, 0.0500g sodium metavanadate and, 0.0500g cetyl trimethylammonium bromide adds
Enter in round-bottomed flask, and to add 9.00mL mass percentage concentration be 30% hydrogenperoxide steam generator, use concentration
Reactant liquor pH to 0.60 is regulated for 6mol/L hydrochloric acid solution.
2) above-mentioned round-bottomed flask is placed in 25 DEG C of water bath with thermostatic control magnetic stirring apparatuss, heating in water bath for reaction, instead
After answering 3h, take 1.00mL reactant liquor, use the extraction of 10.00mL ethyl acetate, obtain containing target product
The organic facies of anisaldehyde；Use trans-anethole and the concentration of anisaldehyde in gas chromatography detection extract organic facies,
Measuring trans-anethole conversion ratio is 54.33%, and the selectivity of anisaldehyde is 35.69%.
3) containing substantial amounts of catalyst and phase transfer catalyst in the aqueous phase obtained after extraction, through boiling off
Use can be continued cycling through after water.
Embodiment 3
The method of a kind of catalyzing hydrogen peroxide oxidation trans-anethole synthesis of natural anisaldehyde, solvent-free and certain
At a temperature of, use sodium metavanadate be catalyst, cetyl trimethylammonium bromide be phase transfer catalyst, urge
The method changing hydrogen peroxide oxidation trans-anethole synthesis of natural anisaldehyde.Specifically comprise the following steps that
1) by 5.00mL trans-anethole, 0.0500g sodium metavanadate and, 0.0500g cetyl trimethyl bromination
Ammonium joins in round-bottomed flask, and to add 9.00mL mass percentage concentration be 30% hydrogenperoxide steam generator, uses
Concentration is that 6mol/L hydrochloric acid solution regulates reactant liquor pH to 0.60.
2) above-mentioned round-bottomed flask is placed in 40 DEG C of water bath with thermostatic control magnetic stirring apparatuss, heating in water bath for reaction, instead
After answering 3h, take 1.00mL reactant liquor, use the extraction of 10.00mL ethyl acetate, obtain containing target product
The organic facies of anisaldehyde；Use trans-anethole and the concentration of anisaldehyde in gas chromatography detection extract organic facies,
Measuring trans-anethole conversion ratio is 98.37%, and the selectivity of anisaldehyde is 47.39%.
3) containing substantial amounts of catalyst and phase transfer catalyst in the aqueous phase obtained after extraction, through boiling off
Use can be continued cycling through after water.
Embodiment 4
The method of a kind of catalyzing hydrogen peroxide oxidation trans-anethole synthesis of natural anisaldehyde, solvent-free and certain
At a temperature of, use sodium metavanadate be catalyst, cetyl trimethylammonium bromide be phase transfer catalyst, urge
The method changing hydrogen peroxide oxidation trans-anethole synthesis of natural anisaldehyde.Specifically comprise the following steps that
1) by 5.00mL trans-anethole, 0.0500g sodium metavanadate and, 0.0500g cetyl trimethyl bromination
Ammonium joins in round-bottomed flask, and to add 5.00mL mass percentage concentration be 30% hydrogenperoxide steam generator, uses
Concentration is that 6mol/L hydrochloric acid solution regulates reactant liquor pH to 0.60.
2) above-mentioned round-bottomed flask is placed in 35 DEG C of water bath with thermostatic control magnetic stirring apparatuss, heating in water bath for reaction, instead
After answering 3h, take 1.00mL reactant liquor, use the extraction of 10.00mL ethyl acetate, obtain containing target product
The organic facies of anisaldehyde；Use trans-anethole and the concentration of anisaldehyde in gas chromatography detection extract organic facies,
Measuring trans-anethole conversion ratio is 81.35%, and the selectivity of anisaldehyde is 42.48%.
3) containing substantial amounts of catalyst and phase transfer catalyst in the aqueous phase obtained after extraction, through boiling off
Use can be continued cycling through after water.
Embodiment 5
The method of a kind of catalyzing hydrogen peroxide oxidation trans-anethole synthesis of natural anisaldehyde, solvent-free and certain
At a temperature of, use sodium metavanadate be catalyst, cetyl trimethylammonium bromide be phase transfer catalyst, urge
The method changing hydrogen peroxide oxidation trans-anethole synthesis of natural anisaldehyde.Specifically comprise the following steps that
1) by 5.00mL trans-anethole, 0.0300g sodium metavanadate and, 0.0500g cetyl trimethyl bromination
Ammonium joins in round-bottomed flask, and to add 9.00mL mass percentage concentration be 30% hydrogenperoxide steam generator, uses
Concentration is that 6mol/L hydrochloric acid solution regulates reactant liquor pH to 0.60.
2) above-mentioned round-bottomed flask is placed in 35 DEG C of water bath with thermostatic control magnetic stirring apparatuss, heating in water bath for reaction, instead
After answering 3h, take 1.00mL reactant liquor, use the extraction of 10.00mL ethyl acetate, obtain containing target product
The organic facies of anisaldehyde；Use trans-anethole and the concentration of anisaldehyde in gas chromatography detection extract organic facies,
Measuring trans-anethole conversion ratio is 75.98%, and the selectivity of anisaldehyde is 30.80%.
3) containing substantial amounts of catalyst and phase transfer catalyst in the aqueous phase obtained after extraction, through boiling off
Use can be continued cycling through after water.
Embodiment 6
The method of a kind of catalyzing hydrogen peroxide oxidation trans-anethole synthesis of natural anisaldehyde, solvent-free and certain
At a temperature of, use sodium metavanadate be catalyst, cetyl trimethylammonium bromide be phase transfer catalyst, urge
The method changing hydrogen peroxide oxidation trans-anethole synthesis of natural anisaldehyde.Specifically comprise the following steps that
1) by 5.00mL trans-anethole, 0.0600g sodium metavanadate and, 0.0500g cetyl trimethyl bromination
Ammonium joins in round-bottomed flask, and to add 9.00mL mass percentage concentration be 30% hydrogenperoxide steam generator, uses
Concentration is that 6mol/L hydrochloric acid solution regulates reactant liquor pH to 0.60.
2) above-mentioned round-bottomed flask is placed in 35 DEG C of water bath with thermostatic control magnetic stirring apparatuss, heating in water bath for reaction, instead
After answering 3h, take 1.00mL reactant liquor, use the extraction of 10.00mL ethyl acetate, obtain containing target product
The organic facies of anisaldehyde；Use trans-anethole and the concentration of anisaldehyde in gas chromatography detection extract organic facies,
Measuring trans-anethole conversion ratio is 96.26%, and the selectivity of anisaldehyde is 55.58%.
3) containing substantial amounts of catalyst and phase transfer catalyst in the aqueous phase obtained after extraction, through boiling off
Use can be continued cycling through after water.
Embodiment 7
The method of a kind of catalyzing hydrogen peroxide oxidation trans-anethole synthesis of natural anisaldehyde, solvent-free and certain
At a temperature of, use sodium metavanadate be catalyst, cetyl trimethylammonium bromide be phase transfer catalyst, urge
The method changing hydrogen peroxide oxidation trans-anethole synthesis of natural anisaldehyde.Specifically comprise the following steps that
1) by 5.00mL trans-anethole, 0.0600g sodium metavanadate and, 0.0300g cetyl trimethyl bromination
Ammonium joins in round-bottomed flask, and to add 9.00mL mass percentage concentration be 30% hydrogenperoxide steam generator, uses
Concentration is that 6mol/L hydrochloric acid solution regulates reactant liquor pH to 0.60.
2) above-mentioned round-bottomed flask is placed in 35 DEG C of water bath with thermostatic control magnetic stirring apparatuss, heating in water bath for reaction, instead
After answering 3h, take 1.00mL reactant liquor, use the extraction of 10.00mL ethyl acetate, obtain containing target product
The organic facies of anisaldehyde；Use trans-anethole and the concentration of anisaldehyde in gas chromatography detection extract organic facies,
Measuring trans-anethole conversion ratio is 76.77%, and the selectivity of anisaldehyde is 33.82%.
3) containing substantial amounts of catalyst and phase transfer catalyst in the aqueous phase obtained after extraction, through boiling off
Use can be continued cycling through after water.
Embodiment 8
The method of a kind of catalyzing hydrogen peroxide oxidation trans-anethole synthesis of natural anisaldehyde, solvent-free and certain
At a temperature of, use sodium metavanadate be catalyst, cetyl trimethylammonium bromide be phase transfer catalyst, urge
The method changing hydrogen peroxide oxidation trans-anethole synthesis of natural anisaldehyde.Specifically comprise the following steps that
1) by 5.00mL trans-anethole, 0.0600g sodium metavanadate and, 0.0600g cetyl trimethyl bromination
Ammonium joins in round-bottomed flask, and to add 9.00mL mass percentage concentration be 30% hydrogenperoxide steam generator, uses
Concentration is that 6mol/L hydrochloric acid solution regulates reactant liquor pH to 0.60.
2) above-mentioned round-bottomed flask is placed in 35 DEG C of water bath with thermostatic control magnetic stirring apparatuss, heating in water bath for reaction, instead
After answering 3h, take 1.00mL reactant liquor, use the extraction of 10.00mL ethyl acetate, obtain containing target product
The organic facies of anisaldehyde；Use trans-anethole and the concentration of anisaldehyde in gas chromatography detection extract organic facies,
Measuring trans-anethole conversion ratio is 95.69%, and the selectivity of anisaldehyde is 31.15%.
3) containing substantial amounts of catalyst and phase transfer catalyst in the aqueous phase obtained after extraction, through boiling off
Use can be continued cycling through after water.
Embodiment 9
The method of a kind of catalyzing hydrogen peroxide oxidation trans-anethole synthesis of natural anisaldehyde, solvent-free and certain
At a temperature of, use sodium metavanadate be catalyst, cetyl trimethylammonium bromide be phase transfer catalyst, urge
The method changing hydrogen peroxide oxidation trans-anethole synthesis of natural anisaldehyde.Specifically comprise the following steps that
1) by 5mL trans-anethole, 0.0600g sodium metavanadate and, 0.0500g cetyl trimethylammonium bromide adds
Enter in round-bottomed flask, and to add 9.00mL mass percentage concentration be 30% hydrogenperoxide steam generator, use concentration
Reactant liquor pH to 0.60 is regulated for 6mol/L hydrochloric acid solution.
2) above-mentioned round-bottomed flask is placed in 35 DEG C of water bath with thermostatic control magnetic stirring apparatuss, heating in water bath for reaction, instead
After answering 1h, take 1.00mL reactant liquor, use the extraction of 10.00mL ethyl acetate, obtain containing target product
The organic facies of anisaldehyde；Use trans-anethole and the concentration of anisaldehyde in gas chromatography detection extract organic facies,
Measuring trans-anethole conversion ratio is 42.58%, and the selectivity of anisaldehyde is 35.65%.
3) containing substantial amounts of catalyst and phase transfer catalyst in the aqueous phase obtained after extraction, through boiling off
Use can be continued cycling through after water.
Embodiment 10
The method of a kind of catalyzing hydrogen peroxide oxidation trans-anethole synthesis of natural anisaldehyde, solvent-free and certain
At a temperature of, use sodium metavanadate be catalyst, cetyl trimethylammonium bromide be phase transfer catalyst, urge
The method changing hydrogen peroxide oxidation trans-anethole synthesis of natural anisaldehyde.Specifically comprise the following steps that
1) by 5.00mL trans-anethole, 0.0600g sodium metavanadate and, 0.0500g cetyl trimethyl bromination
Ammonium joins in round-bottomed flask, and to add 9.00mL mass percentage concentration be 30% hydrogenperoxide steam generator, uses
Concentration is that 6mol/L hydrochloric acid solution regulates reactant liquor pH to 0.60.
2) above-mentioned round-bottomed flask is placed in 35 DEG C of water bath with thermostatic control magnetic stirring apparatuss, heating in water bath for reaction, instead
After answering 5h, take 1.00mL reactant liquor, use the extraction of 10.00mL ethyl acetate, obtain containing target product
The organic facies of anisaldehyde；Use trans-anethole and the concentration of anisaldehyde in gas chromatography detection extract organic facies,
Measuring trans-anethole conversion ratio is 100%, and the selectivity of anisaldehyde is 34.62%.
3) containing substantial amounts of catalyst and phase transfer catalyst in the aqueous phase obtained after extraction, through boiling off
Use can be continued cycling through after water.
Claims (1)
1. the method for a catalyzing hydrogen peroxide oxidation trans-anethole synthesis of natural anisaldehyde, it is characterised in that
Using sodium metavanadate under solvent-free and certain temperature conditions is that catalyst, cetyl trimethylammonium bromide are
Phase transfer catalyst, the method for catalyzing hydrogen peroxide oxidation trans-anethole synthesis of natural anisaldehyde, specifically comprise the following steps that
1) by 5mL trans-anethole, 0.0300～0.0600g sodium metavanadate and 0.0300～0.0600g hexadecane
Base trimethylammonium bromide joins in round-bottomed flask, and to add 5～11mL mass percentage concentration be 30% mistake
Hydrogen peroxide solution, is that 6mol/L hydrochloric acid solution regulates reactant liquor pH to 0.60 by concentration；
2) above-mentioned round-bottomed flask is placed in 25～40 DEG C of water bath with thermostatic control magnetic stirring apparatuss, heating in water bath for reaction,
After reaction 1～5h, take 1.00ml reactant liquor, use the extraction of 10.00ml ethyl acetate, obtain containing mesh
The organic facies of mark product anisaldehyde；Use gas chromatography detection extract organic facies, measure trans-anethole conversion ratio
And the selectivity of anisaldehyde；
3) containing substantial amounts of catalyst and phase transfer catalyst in the aqueous phase obtained after extraction, through boiling off
Use can be continued cycling through after water.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4814512A (en) * | 1985-12-20 | 1989-03-21 | Nippon Shokubai Kagaku Kogyo | Method for the production of p-methoxybenzaldehyde |
| CN103224446A (en) * | 2013-05-15 | 2013-07-31 | 广西民族大学 | Method for preparing natural anisaldehyde from anethol |
-
2016
- 2016-05-05 CN CN201610292632.9A patent/CN105924340A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4814512A (en) * | 1985-12-20 | 1989-03-21 | Nippon Shokubai Kagaku Kogyo | Method for the production of p-methoxybenzaldehyde |
| CN103224446A (en) * | 2013-05-15 | 2013-07-31 | 广西民族大学 | Method for preparing natural anisaldehyde from anethol |
Non-Patent Citations (3)
| Title |
|---|
| BAOCHUN MA ET AL.: "《Solvent-free selective oxidation of C H bonds of toluene and substituted toluene to aldehydes by vanadium-substituted polyoxometalate catalyst》", 《JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL》 * |
| RONNY NEUMANN ET AL.: "《Oxidation of alkylaromatic compounds with hydrogen peroxide catalyzed by mixed addenda Keggin heteropolyanions》", 《JOURNAL OF MOLECULAR CATALYSIS》 * |
| 黄文榜等: "《相转移催化高锰酸钾氧化茴香脑制备茴香醛》", 《化学世界》 * |
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